FI66877C - FRAMEWORK OF ORGANIC TRIHALOGENTEN (IV) -FOERENINGAR - Google Patents
FRAMEWORK OF ORGANIC TRIHALOGENTEN (IV) -FOERENINGAR Download PDFInfo
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- FI66877C FI66877C FI801644A FI801644A FI66877C FI 66877 C FI66877 C FI 66877C FI 801644 A FI801644 A FI 801644A FI 801644 A FI801644 A FI 801644A FI 66877 C FI66877 C FI 66877C
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- Prior art keywords
- compound
- tin
- olefin
- process according
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- Prior art date
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- QHGNHLZPVBIIPX-UHFFFAOYSA-N tin(ii) oxide Chemical compound [Sn]=O QHGNHLZPVBIIPX-UHFFFAOYSA-N 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 20
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 16
- 150000001336 alkenes Chemical class 0.000 claims description 15
- 150000001875 compounds Chemical class 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 15
- -1 tin (II) compound Chemical class 0.000 claims description 15
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 12
- 238000002360 preparation method Methods 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 6
- FUSUHKVFWTUUBE-UHFFFAOYSA-N vinyl methyl ketone Natural products CC(=O)C=C FUSUHKVFWTUUBE-UHFFFAOYSA-N 0.000 claims description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 4
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims description 3
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 230000003213 activating effect Effects 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- PBZROIMXDZTJDF-UHFFFAOYSA-N hepta-1,6-dien-4-one Chemical compound C=CCC(=O)CC=C PBZROIMXDZTJDF-UHFFFAOYSA-N 0.000 claims description 2
- LNMQRPPRQDGUDR-UHFFFAOYSA-N hexyl prop-2-enoate Chemical compound CCCCCCOC(=O)C=C LNMQRPPRQDGUDR-UHFFFAOYSA-N 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- MCVVUJPXSBQTRZ-ONEGZZNKSA-N methyl (e)-but-2-enoate Chemical compound COC(=O)\C=C\C MCVVUJPXSBQTRZ-ONEGZZNKSA-N 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000012429 reaction media Substances 0.000 claims description 2
- 101100450129 Caenorhabditis elegans hal-3 gene Proteins 0.000 claims 1
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- 239000007858 starting material Substances 0.000 claims 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 14
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 8
- 239000000460 chlorine Substances 0.000 description 7
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 4
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 4
- 229910000039 hydrogen halide Inorganic materials 0.000 description 3
- 239000012433 hydrogen halide Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XDOFQFKRPWOURC-UHFFFAOYSA-N 16-methylheptadecanoic acid Chemical compound CC(C)CCCCCCCCCCCCCCC(O)=O XDOFQFKRPWOURC-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical group COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000002798 polar solvent Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 241000208152 Geranium Species 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 150000001356 alkyl thiols Chemical class 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 239000012230 colorless oil Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 125000001891 dimethoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- PKHHQFAULPTXEW-UHFFFAOYSA-N ethane;prop-2-enoic acid Chemical compound CC.OC(=O)C=C PKHHQFAULPTXEW-UHFFFAOYSA-N 0.000 description 1
- XHIOOWRNEXFQFM-UHFFFAOYSA-N ethyl prop-2-enoate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(=O)C=C XHIOOWRNEXFQFM-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 150000002688 maleic acid derivatives Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical group 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- IPCSVZSSVZVIGE-UHFFFAOYSA-N palmitic acid group Chemical group C(CCCCCCCCCCCCCCC)(=O)O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229960001860 salicylate Drugs 0.000 description 1
- 238000010517 secondary reaction Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000001119 stannous chloride Substances 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000003039 volatile agent Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/56—Organo-metallic compounds, i.e. organic compounds containing a metal-to-carbon bond
- C08K5/57—Organo-tin compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/22—Tin compounds
- C07F7/2208—Compounds having tin linked only to carbon, hydrogen and/or halogen
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
Description
I- M M4. KUULUTUSJULKAISU , , n π n jttfit W (11)utlAggningsskript 668 77 SSt C rater, li I työnne tty 10 12 1934 ^ ” Patent oeddelat v (S1) Kv.lk/DK.0.3 C 07 F 7/22 SUOMI—FINLAND W 801644 (22) HikwniipiMI — AiwMnHngri»| 21.05.80 (FI) (23) Aih>M»i—<aw^i>mi| 21.05.80 (41) TuMhcHIUMfcH — BtMtoff«M*x 24.11.80I- M M4. NOTICE OF PUBLICATION,, n π n jttfit W (11) utlAggningsskript 668 77 SSt C rater, li I pusen tty 10 12 1934 ^ ”Patent oeddelat v (S1) Kv.lk/DK.0.3 C 07 F 7/22 FINLAND — FINLAND W 801644 (22) HikwniipiMI - AiwMnHngri »| 21.05.80 (FI) (23) Aih> M »i— <aw ^ i> mi | 21.05.80 (41) TuMhcHIUMfcH - BtMtoff «M * x 24.11.80
Patentti- ja rak(atarihallitut riltniirltrri>>nrn )t ‘-»I .„n[lll1,n pvm. —Patent and rak (patented riltniirltrri >> nrn) t '- »I.„ N [lll1, n pvm. -
Patanfc· och raglataratyrelaen ' Amdfcm nHurt ed> eUMta pebteerri 31.O8.84 (32)(33)(31) eo«o«k*is—teglrd priorlut 23.05.79Patanfc · och raglataratyrelaen 'Amdfcm nHurt ed> eUMta pebteerri 31.O8.84 (32) (33) (31) eo «o« k * is — teglrd priorlut 23.05.79
Ranska-Frankrike(FR) 7913108 (71) SociStS Nationale Elf Aquitaine, Tour Aquitaine, 92400 Courbevoie, Ranska-Frankrike(FR) (72) Michel Foure, Artix, Ranska-Frankrike(FR) (74) Berggren Oy Ab (54) Menetelmä orgaanisten trihalogeeni-tina(IV)-yhdisteiden valmistamiseksi - Forfarande för framstäl1 ning av organiska trihalogentenn(IV)--fören i ngar Tämä keksintö koskee parannettua menetelmää organotina(IV)-trihalogenidien valmistamiseksi lähtemällä tina (II)-yhdisteestä, jonka annetaan reagoida olefiiniyhdisteen kanssa, jossa on aktivoiva karbonyyliryhmä hiili-hiili-kaksoissidoksen vieressä, vetyhapon, kuten kloorivetyhapon läsnäollessa. Organotina(IV)-trihalogenidit ovat tärkeitä raaka-aineita valmistettaessa tinan orgaanisia yhdisteitä, joita käytetään stabiloivina aineina nimenomaan polyvinyyliklorideissa.France-France (FR) 7913108 (71) SociStS Nationale Elf Aquitaine, Tour Aquitaine, 92400 Courbevoie, France-France (FR) (72) Michel Foure, Artix, France-France (FR) (74) Berggren Oy Ab (54) This invention relates to an improved process for the preparation of organotin (IV) trihalides starting from a tin (II) compound which is reacted with an olefin compound having an activating carbonyl group adjacent to the carbon-carbon double bond in the presence of a hydrogen acid such as hydrochloric acid. Organotin (IV) trihalides are important raw materials in the preparation of organotin compounds, which are used as stabilizers specifically in polyvinyl chlorides.
Organotina(IV)-trihalogenidien hyvin tunnetun merkityksen ansiosta teollisuudessa on näiden aineiden valmistamista tutkittu hyvin paljon. Siten esimerkiksi ranskalaisessa patentissa 2 285 392 selostetaan menetelmää, joka perustuu tinahalogenidin ja sellaisen olefiinin reaktioon, jossa on hiili-hiili-kaksoissidoksen vieressä karbonyyliryhmä, ja reaktiossa on mukana halogeenivetyä. Tämä reaktio tapahtuu käytännössä jossakin polaarisessa liuottimessa kuten alkyy-lieetterissä tai edullisimmin dietyylieetterissä. Tämä menetelmä vaatii siis liuottimen poistamisen ja puhtaan tuotteen uuttamisen jonkin toisen liuottimen avulla.Due to the well-known importance of organotin (IV) trihalides, the preparation of these substances has been extensively studied in industry. Thus, for example, French Patent 2,285,392 discloses a process based on the reaction of a tin halide and an olefin having a carbonyl group adjacent to a carbon-carbon double bond, in which hydrogen halide is involved. This reaction takes place in practice in a polar solvent such as an alkyl ether or, most preferably, diethyl ether. This method therefore requires the removal of the solvent and the extraction of the pure product with another solvent.
2 668772,66877
Nyt on keksitty keino, millä voidaan välttää näitä hankaluuksia ja työskennellä täysin ilman liuotinta ja on havaittu, että organotina(IV)-trihalogenidien tuotokset ovat parantuneet.A way has now been devised to avoid these inconveniences and to work completely without solvent, and it has been found that the yields of organotin (IV) trihalides have improved.
Keksinnön mukaiselle menetelmälle organotina (IC)-trihalogenidien valmistamiseksi on tunnusomaista että, reaktioväli-aineessa ei ole lainkaan vierasta liuotinta, vaan se sisältää ylimäärän olefiinia, ja tämä ylimäärä on ainakin 0,5 moolia tina(II)-yhdisteen moolia kohti.The process according to the invention for the preparation of organotin (IC) trihalides is characterized in that the reaction medium has no foreign solvent at all, but contains an excess of olefin, and this excess is at least 0.5 moles per mole of stannous compound.
Tina(II)-yhdiste voi olla tina(II)-halogenidi (kloridi, bromidi, jodidi) mutta myös, vieläpä edullisemmin se voi olla tina (II)-oksidi SnO, mieluimmin hyvin hienojakoisessa muodossa.The tin (II) compound may be a tin (II) halide (chloride, bromide, iodide) but also, even more preferably, it may be a tin (II) oxide SnO, preferably in a very fine form.
Olefiiniyhdisteellä on seuraava kaavaThe olefin compound has the following formula
^2 R^ 2 R
, ^R3 R. - C - C = C 1 \ O R4 jossa R2, R3 ja R^ esittävät vetyä tai alkyylihiilivetyjäännöstä, joka sisältää 1-3 hiiliatomia ja R^ esittää alkyyli-ryhmää, hydroksyyliä tai hiilivetyryhmää, joka sisältää happea. Saatujen organotina(IV)-trihalogenidien kaava on: R3 R2, R 3 R 3 - C - C = C 1 O 4 wherein R 2, R 3 and R 4 represent hydrogen or an alkyl hydrocarbon residue containing 1 to 3 carbon atoms and R 4 represents an alkyl group, a hydroxyl or a hydrocarbon group containing oxygen. The organotin (IV) trihalides obtained have the formula: R3 R2
I II I
Hal^Sn - C - C - CO R.Hal ^ Sn - C - C - CO R.
J ' I 1 R4 hJ '1 R4 h
Olefiineista, jotka vastaavat edellä olevaa kaavaa, voidaan mainita seuraavat: metyyliakrylaatti, etyyliakrylaatti, heksyyliakrylaatti, akryylihappo, vinyylimetyyliketoni, metyylikrotonaatti.Among the olefins corresponding to the above formula, the following can be mentioned: methyl acrylate, ethyl acrylate, hexyl acrylate, acrylic acid, vinyl methyl ketone, methyl crotonate.
Halogeenivedyn ja tina(II)-halogenidin halogeeni voi olla: kloori, bromi, jodi tai vieläpä fluori, mutta se on etupäässä kloori; .käytetään siis etupäässä kloorivetyhappoa ja tina(II)-kloridia.Halogen of hydrogen halide and stannous halide may be: chlorine, bromine, iodine or even fluorine, but it is primarily chlorine; Thus, hydrochloric acid and stannous chloride are used primarily.
3 668773,66877
Olefiinia käytetään ylimäärä suhteessa tina (II) -yhdisteeseen ; se on välillä 1,5 mol - 6 mol tina(II)-yhdisteen yhtä moolia kohti. Erinomaisia tuloksia on saatu silloin, kun tämä määrä on 3,5 - 4,5 mol, ja mieluimmin 4 mol olefiinia tina(II)-yhdisteen yhtä moolia kohti.Olefin is used in excess relative to the tin (II) compound; it is between 1.5 mol and 6 mol per one mol of the stannous compound. Excellent results have been obtained when this amount is 3.5 to 4.5 moles, and preferably 4 moles of olefin per mole of tin (II) compound.
Ei ollut lainkaan itsestään selvää, että ilman polaarista liuotinta ja olefiiniylimäärän kanssa suoritettava reaktio johtaisi hyviin tuloksiin; ranskalaisessa patentissa n:o 3 368 494. joka koskee diorganotina(IV)-dihalogenidien valmistamista antamalla tinan, kloorivetyhapon ja karbonyyliryhmien aktivoimien ole-fiinien reagoida keskenään, ilmoitetaan nimittäin, että jos ole-fiini toimii samanaikaisesti myös liuottimena, aiheutuu siitä hyvin huomattavassa määrin sekundäärisiä polymeroitumisreaktioi-ta. Oli siis täysin yllättävä tulos, että keksinnön mukaisessa menetelmässä, jossa työskennellään ilman liuotinta ja olefiini-ylimäärää käyttäen, päästään niihin erinomaisiin tuloksiin, jotka on selostettu esimerkeissä.It was not at all self-evident that the reaction with a polar solvent and with an excess of olefin would lead to good results; French Patent No. 3,368,494, which relates to the preparation of diorganotin (IV) dihalides by reacting olefins activated by tin, hydrochloric acid and carbonyl groups, states that if olefin also acts as a solvent at the same time, it causes very significant secondary reactions; polymeroitumisreaktioi-O. It was thus a completely surprising result that the process according to the invention, which is carried out without solvent and with an excess of olefin, gives the excellent results described in the examples.
Halogeenivety johdetaan kaasuvirran muodossa. Reaktiolämpötila on välillä 15-70°C; se on edullisimmin noin 25-30°C; menetelmä suoritetaan atmosfäärin paineessa.Hydrogen halide is passed in the form of a gas stream. The reaction temperature is between 15 and 70 ° C; it is most preferably about 25-30 ° C; the method is performed at atmospheric pressure.
Tämän keksinnön mukaisen menetelmän mukaan valmistetut organo-tina(II)-yhdisteet voidaan muuttaa, kuten on selostettu ranskalaisessa patentissa n:o 2 285 392 prgahotina(IV)-yhdisteiksi, jotka stabiloivat halogenoituja vinyylipolymeerejä, antamalla näiden trihalogeeni- tina(II)-yhdisteiden reagoida orgaanisten rasvahappojen, maleiinihappoestereiden, alkyylitioleiden tai merkaptoesterei-den kanssa, jolloin saadaan kaavan RSnA^ mukaisia yhdisteitä, joissa R esittää lähtöaineena käytetystä olefiinista peräisin olevaa ryhmää ja A esittää orgaanisen hapon jäännöstä, joka voi olla ryhmä -S(CI^)nCOO-alkyyli, jossa n = 1 tai 2, -S-alkyyli, -OCO-alkyyli tai OCOH=CHCOO-alkyyli.The organotin (II) compounds prepared according to the process of this invention can be converted, as described in French Patent No. 2,285,392, into prgahotina (IV) compounds which stabilize halogenated vinyl polymers by giving these trihalogenate (II) compounds react with organic fatty acids, maleic acid esters, alkylthiols or mercaptoesters to give compounds of formula RSnA 2 wherein R represents a group derived from the starting olefin and A represents an organic acid residue which may be a group -S (C 1-4) n COO-alkyl , where n = 1 or 2, -S-alkyl, -OCO-alkyl or OCOH = CHCOO-alkyl.
Kyseessä olevassa keksinnössä selostetun menetelmän mukaan valmistettuja organotina(IV)-yhdisteitä voidaan muuttaa myös organo-tina(IV)-yhdisteiksi, jofcka stabiloivat halogeenivinyylihartseja, kuten on selostettu suomalaisessa patenttihakemuksessa 801 645, nimittäin antamalla trihalogeenitina(IV)- 4 66877 yhdisteiden reagoida merkaptoalkyyliestereiden HS(CH0) OCR..The organotin (IV) compounds prepared according to the process described in the present invention can also be converted to organotin (IV) compounds which stabilize halovinyl resins, as described in Finnish patent application 801 645, namely by giving the trihalogenate (IV) -6,66877 of the compounds (CH0) OCR ..
* n „ b 0 kanssa, joissa Rg on alkyyli, joka sisältää 1-18 hiiliatomia* se voi olla mistä tahansa alifaattisesta mono- tai dihaposta peräisin, kuitenkin pidetään parhaina estereitä, jotka johtuvat rasvahapoista, varsinkin kapryyli-, pelargoni-, kapriini-, undekaani-, lauriini-, myristiini-, palmitiini-, steariini-, isosteariinihaposta tai tällaisten happojen seoksista.* n „b 0 where Rg is alkyl containing 1-18 carbon atoms * it can be derived from any aliphatic mono- or diacid, however, esters derived from fatty acids, especially caprylic, geranium, capric, undecanoic, lauric, myristic, palmitic, stearic, isostearic acid or mixtures of such acids.
Keksintöä valaistaan seuraavien esimerkkien avulla.The invention is illustrated by the following examples.
Esimerkki 1 500 ml:n vetoiseen kolmikaulakolviin, joka on varustettu sekoittajalla, lämpömittarilla, jäähdyttäjällä, putkella kaasun johtamista varten, ja ulkopuolisella jäähdytyssysteemillä, lisätään 33,8 g (0,25 mol) tina(II)-oksidia 86 g (1 mol) metyyliakry-laattia. Sekoitetaan voimakkaasti ja lisätään kolviin kloori-vetyhappoa kaasun muodossa siten, että se kulutetaan sitä mukaa kuin sitä lisätään. Lämpötila pidetään välillä 25° - 30°C. Kun reaktioseos ei enää absorboi HCl:ä, tislataan metyyliakry-laatin ylimäärä. Jäljelle jää jäännös, joka puhdistetaan liuottamalla kloroformiin, dekantoimalla, kuivaamalla kalsiumklo-ridin avulla ja haihduttamalla liuotin. Saadaan 77,5 g eli 99 %:n tuotos laskettuna tina(II)-oksidista, kiteistä valkeata yhdistettä, joka vastaa kaavaa Cl^SnCH^C^COOCH^. sen sp. on 71°C. ·Example 1 To a 500 ml three-necked flask equipped with a stirrer, thermometer, condenser, conduit, and external cooling system is added 33.8 g (0.25 mol) of stannous oxide 86 g (1 mol). metyyliakry-salicylate. Stir vigorously and add the hydrochloric acid in the form of gas to the flask so that it is consumed as it is added. The temperature is maintained between 25 ° and 30 ° C. When the reaction mixture no longer absorbs HCl, excess methyl acrylate is distilled off. The residue remains, which is purified by dissolving in chloroform, decanting, drying over calcium chloride and evaporating the solvent. 77.5 g or 99% yield based on tin (II) oxide of a crystalline white compound corresponding to the formula Cl 2 SnCH 2 Cl 2 COOCH 2 are obtained. sen sp. is 71 ° C. ·
Esimerkki 2Example 2
Laitteisto ja työskentelytapa ovat samat kuin esimerkissä 1, mutta metyyliakrylaatti korvataan 100,3 g:lla (1 mol) etyyli-akrylaattia. Saadaan 82,4 g väritöntä öljyä, joka indentifioi-daan infrapunasäteiden avulla yhdisteeksi Cl2SnCH2CH2C02C2H5. Tätä yhdistettä saadaan 100 %:n tuotos.The apparatus and procedure are the same as in Example 1, but the methyl acrylate is replaced by 100.3 g (1 mol) of ethyl acrylate. 82.4 g of a colorless oil are obtained, which is identified by infrared rays as the compound Cl2SnCH2CH2CO2CO2H5. This compound gives a 100% yield.
Esimerkki 3Example 3
Laitteisto ja työskentelytapa ovat samat kuin esimerkissä 1 ja kolviin pannaan 67,5 g (0,5 mol) tina(II)-oksidia ja 250 g (2 mol) metyylivinyyliketoniaj sekoitetaan voimakkaasti ja johdetaan joukkoon HCl:ä kaasun muodssa. Kun reaktio on päättynyt, tislataan metyylivinyyliketonin ylimäärä. Aine puhdiste- 5 66877 taan kloroformissa ja saadaan 144 g eli 98 %:n tuotos valkeata kiteistä ainetta, joka identifioidaan spektroskoopin avulla yhdisteeksi Cl^SnCH-^d^COCH-j.The apparatus and procedure are the same as in Example 1, and 67.5 g (0.5 mol) of stannous oxide are introduced into the flask and 250 g (2 mol) of methyl vinyl ketone are stirred vigorously and HCl is introduced into the gas. When the reaction is complete, the excess methyl vinyl ketone is distilled off. The material is purified in chloroform to give 144 g, or 98% yield, of a white crystalline material which is identified spectroscopically as Cl 2 SnCH-d 2 COCH-j.
Esimerkki 4Example 4
Työskennellään kuten edellä olevissa esimerkeissä: kolviin pannaan 67,5 g (0,5 mol) tina(II)-oksidia ja 144 g (2 mol) akryyli-happoa. Johdetaan kaasumaista HCl:ä niin nopeasti kuin absorptio antaa myöten ja pidetään lämpötila välillä 25° - 30°C. Absorption loputtua akryylihapon ylimäärä tislataan vakuumissa. Kiinteä jäännös puhdistetaan kloroformilla ja tislauksen jälkeen saadaan 146 g valkeata kiinteätä ainetta, jonka kaava on identifioitu spektrograafisesti ClgSnCI^CHjCOOH: ksi. Tuotos: 98 % laskettuna tina (II)-oksidista.Work as in the above examples: 67.5 g (0.5 mol) of stannous oxide and 144 g (2 mol) of acrylic acid are placed in the flask. Gaseous HCl is introduced as rapidly as the absorption allows and the temperature is maintained between 25 ° and 30 ° C. When the absorption is complete, the excess acrylic acid is distilled off in vacuo. The solid residue is purified by chloroform and, after distillation, 146 g of a white solid of the formula identified spectrographically as ClgSnCl2CH2COOH are obtained. Yield: 98% based on tin (II) oxide.
Esimerkki 5Example 5
Työskennellään kuten esimerkissä 1, mutta käyttäen liuotinta, eikä metyyliakrylaatin ylimäärää. Kolmikaulakolviin pannaan 67,5 g (0,5 mol) tina(II)-oksidia, 43g(0,5 mol) metyyliakrylaat-tia ja 200 ml dietyylieetteriä. Sekoitetaan voimakkaasti ja johdetaan kloorivetykaasua sillä nopeudella kuin sitä kuluu ja pidetään lämpötila välillä 25° - 30°C. Eetteri haihdutetaan vakuumissa. Aine liuotetaan 250 ml:an kloroformia. Dekantoi-daan ja kuivataan orgaaninen faasi Cl2Ca:n avulla, suodatetaan ja poistetaan liuotin ja haihtuvat aineet vakuumissa. Saadaan 141 g (eli 90 %:n tuotos yksinomaan tina(II)-oksidista laskettuna) valkeata ainetta, joka uudelleentislattuna sulaa 73°C:ssa. Se vastaa kaavaa Cl^SnCI^CI^CC^CH^.Work as in Example 1, but using a solvent and not excess methyl acrylate. 67.5 g (0.5 mol) of stannous oxide, 43 g (0.5 mol) of methyl acrylate and 200 ml of diethyl ether are placed in a three-necked flask. Stir vigorously and introduce hydrogen chloride gas at the rate at which it is consumed and maintain the temperature between 25 ° and 30 ° C. The ether is evaporated in vacuo. The substance is dissolved in 250 ml of chloroform. The organic phase is decanted and dried over Cl2Cl2, filtered and the solvent and volatiles are removed in vacuo. 141 g (i.e. a 90% yield based on tin (II) oxide alone) of a white substance are obtained which, after redistillation, melts at 73 ° C. It corresponds to the formula Cl ^ SnCl ^ Cl ^ CC ^ CH 2.
Esimerkit 6-8 Nämä kokeet suoritetaan menetelmän mukaan, joka on selostettu esimerkissä 5, eli aikaisemman tekniikan mukaisesti, käyttäen liuotinta eikä olefiinin ylimäärää, tai vain hyvin pienen ylimäärän kanssa. Esimerkki 6 suoritetaan SnCl2:n kanssa, ja liuotin on dimetoksietaani; esimerkki 7 suoritetaan käyttäen SnC^ta ja hyvin pientä olefiiniylimäärää ja dietyylieetteriä liuottimena; esimerkki 8 suoritetaan käyttäen SnO:a ja liuottimena dimetoksietaania.Examples 6-8 These experiments are carried out according to the method described in Example 5, i.e. according to the prior art, using a solvent and not an excess of olefin, or only with a very small excess. Example 6 is performed with SnCl 2 and the solvent is dimethoxyethane; Example 7 is performed using SnCl 2 and a very small excess of olefin and diethyl ether as solvent; Example 8 is performed using SnO and dimethoxyethane as solvent.
6 668776 66877
TAULUKKO ITABLE I
Esimerk- Olefii- Tina(II)- Moolisuhde Liuotin Tuotos % ki n:o ni (1) yhdiste (2) (1)/(2) ^ Metyyli- SnO 4 Ei mitään 99 akrylaatti 2 Etyyli- " " " 100 akrylaatti 3 Srt) 4 Ei mitään 98 ketoni 4 Akrjggli- SnD 4 Ei mitään 98 5 Metyyli- SnO 1 Dietyyli- 90 akrylaatti eetteri . Metyyli- SnCl» 1 Dimetoksi- 89 6 akrylaatti 2 etaani 7 Etyyli- SnCl2 1,2 Dietyyli- 79 akrylaatti eetteri g Etyyli- SnO 1 Dimetoksi- 92 akrylaatti etaaniExample Olefin (Tin) Molar Ratio Solvent Yield% No. (1) Compound (2) (1) / (2) Methyl SnO 4 None 99 Acrylate 2 Ethyl Acrylate 3 Srt) 4 None 98 ketone 4 Acrylic SnD 4 None 98 5 Methyl SnO 1 Diethyl 90 acrylate ether Methyl SnCl 1 Dimethoxy 89 6 acrylate 2 ethane 7 Ethyl SnCl 2 1,2 Diethyl 79 acrylate ether g Ethyl SnO 1 Dimethoxy-92 acrylate ethane
Esimerkkien 1-8 tulokset on koottu taulukkoon I. Verrattaessa tuloksia voidaan todeta, että parhaat tuotokset saadaan silloin kun menetelmä toteutetaan menettelytavan mukaan, joka on selostettu kyseessä olevassa patenttihakemuksessa.The results of Examples 1 to 8 are summarized in Table I. Comparing the results, it can be seen that the best yields are obtained when the method is carried out according to the procedure described in the present patent application.
Claims (6)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR7913108A FR2458554A1 (en) | 1979-05-23 | 1979-05-23 | PROCESS FOR THE PREPARATION OF ORGANOSTANNIC TRIHALOGENURES |
| FR7913108 | 1979-05-23 |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| FI801644A FI801644A (en) | 1980-11-24 |
| FI66877B FI66877B (en) | 1984-08-31 |
| FI66877C true FI66877C (en) | 1984-12-10 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| FI801644A FI66877C (en) | 1979-05-23 | 1980-05-21 | FRAMEWORK OF ORGANIC TRIHALOGENTEN (IV) -FOERENINGAR |
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| Country | Link |
|---|---|
| US (1) | US4324737A (en) |
| EP (1) | EP0021032B1 (en) |
| JP (1) | JPS55157590A (en) |
| AR (1) | AR224531A1 (en) |
| AU (1) | AU536559B2 (en) |
| BR (1) | BR8003216A (en) |
| CA (1) | CA1139310A (en) |
| DE (1) | DE3062262D1 (en) |
| ES (1) | ES8105335A1 (en) |
| FI (1) | FI66877C (en) |
| FR (1) | FR2458554A1 (en) |
| GR (1) | GR68551B (en) |
| IL (1) | IL60142A0 (en) |
| IN (1) | IN154329B (en) |
| NO (1) | NO801536L (en) |
| PT (1) | PT71267A (en) |
| YU (1) | YU136380A (en) |
| ZA (1) | ZA803046B (en) |
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| PL147517B1 (en) * | 1985-09-25 | 1989-06-30 | Politechnika Warszawska | Method of obtaining cyanoorganic compounds |
| PT816367E (en) * | 1996-06-25 | 2001-09-28 | Crompton Gmbh | MONOVINILLE TRI-HALOGENETS, TIN AND PROCESS FOR PREPARATION |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL7412230A (en) * | 1974-09-16 | 1976-03-18 | Akzo Nv | PROCESS FOR THE PREPARATION OF ORGANOTINTRI HALOGENIDES. |
| US4105684A (en) * | 1974-09-16 | 1978-08-08 | Akzo N.V. | Process for the preparation of organotin trihalides |
| NL7503116A (en) * | 1975-03-17 | 1976-09-21 | Akzo Nv | PROCEDURE FOR PREPARING ORGANOTIN DIHALOGENIDES AND ORGANOTIN STABILIZERS DERIVED FROM THEREOF. |
| US4080363A (en) * | 1975-03-17 | 1978-03-21 | Akzo N.V. | Process for making organotin dihalides and trihalides and stabilizers prepared therefrom |
| DE2648107B1 (en) * | 1976-10-23 | 1978-02-02 | Schering Ag | Process for the preparation of diorganotin dihalides |
| DE2735757A1 (en) * | 1977-08-09 | 1979-02-15 | Hoechst Ag | NEW ORGANOCIN HALOGENIDES AND PROCESS FOR THEIR PRODUCTION |
| EP0002019A1 (en) * | 1977-11-14 | 1979-05-30 | Ciba-Geigy Ag | Methods for the preparation of organotin compounds |
-
1979
- 1979-05-23 FR FR7913108A patent/FR2458554A1/en active Granted
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1980
- 1980-05-19 IN IN364/DEL/80A patent/IN154329B/en unknown
- 1980-05-20 DE DE8080102793T patent/DE3062262D1/en not_active Expired
- 1980-05-20 US US06/151,642 patent/US4324737A/en not_active Expired - Lifetime
- 1980-05-20 EP EP80102793A patent/EP0021032B1/en not_active Expired
- 1980-05-20 PT PT71267A patent/PT71267A/en unknown
- 1980-05-21 AU AU58635/80A patent/AU536559B2/en not_active Ceased
- 1980-05-21 FI FI801644A patent/FI66877C/en not_active IP Right Cessation
- 1980-05-21 YU YU01363/80A patent/YU136380A/en unknown
- 1980-05-22 IL IL60142A patent/IL60142A0/en unknown
- 1980-05-22 GR GR62024A patent/GR68551B/el unknown
- 1980-05-22 ZA ZA00803046A patent/ZA803046B/en unknown
- 1980-05-22 CA CA000352536A patent/CA1139310A/en not_active Expired
- 1980-05-22 ES ES491738A patent/ES8105335A1/en not_active Expired
- 1980-05-22 JP JP6718780A patent/JPS55157590A/en active Pending
- 1980-05-22 NO NO801536A patent/NO801536L/en unknown
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| Publication number | Publication date |
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| AU536559B2 (en) | 1984-05-10 |
| ES491738A0 (en) | 1981-05-16 |
| FI801644A (en) | 1980-11-24 |
| US4324737A (en) | 1982-04-13 |
| JPS55157590A (en) | 1980-12-08 |
| EP0021032A1 (en) | 1981-01-07 |
| PT71267A (en) | 1980-06-01 |
| AU5863580A (en) | 1980-11-27 |
| YU136380A (en) | 1983-02-28 |
| ES8105335A1 (en) | 1981-05-16 |
| GR68551B (en) | 1982-01-18 |
| IL60142A0 (en) | 1980-07-31 |
| EP0021032B1 (en) | 1983-03-09 |
| DE3062262D1 (en) | 1983-04-14 |
| FI66877B (en) | 1984-08-31 |
| FR2458554B1 (en) | 1982-07-09 |
| NO801536L (en) | 1980-11-24 |
| FR2458554A1 (en) | 1981-01-02 |
| CA1139310A (en) | 1983-01-11 |
| AR224531A1 (en) | 1981-12-15 |
| BR8003216A (en) | 1980-12-30 |
| IN154329B (en) | 1984-10-20 |
| ZA803046B (en) | 1981-08-26 |
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